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Record W2927300499 · doi:10.1039/c9cp01263j

Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays

2019· article· en· W2927300499 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenuePhysical Chemistry Chemical Physics · 2019
Typearticle
Languageen
FieldPhysics and Astronomy
TopicX-ray Spectroscopy and Fluorescence Analysis
Canadian institutionsJoint Attosecond Science Laboratory
FundersEuropean Regional Development Fund
KeywordsTransition metalSPHERESUltrashort pulseChemical physicsMaterials scienceMetalCrystallographyNanotechnologyChemistryPhysicsOpticsLaserMetallurgy

Abstract

fetched live from OpenAlex

The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry. Manipulating the organization around transition metal ions with covalent and supramolecular interactions is a general strategy that underlies most synthetic protocols. Achieving similar control for photoexcited molecular complexes is necessary to advance the design of light-driven functionalities. This objective calls for monitoring the ultrafast dynamics of the primary (1-CS) and the secondary (2-CS) coordination spheres on the atomic scale, which remains to date an important experimental challenge for short-lived species. In this work, transient wide-angle scattering of hard X-rays (25 keV) is employed with state-of-the-art AIMD simulations in order to visualize the 1-CS (solute-only) and the 2-CS (solvation cage) of the photoinduced high-spin (HS) state for [Fe(bpy)3]2+ (bpy = 2,2'-bipyridine) in aqueous solution. Correlating this structural information in real-space reveals the interlacing of the two CS, which in turn explains why solvation affects the photoinduced electronic and structural dynamics in this class of complexes. More generally, these results obtained for a prominent prototypical system in ultrafast X-ray sciences demonstrate the unique perspectives offered by this technique to gain the crucial knowledge about the multiscale solvation dynamics that is currently missing for controlling the solute-solvent interactions in advanced functional nano and biomaterials employed for photoconversion.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.010
Threshold uncertainty score0.914

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.008
GPT teacher head0.237
Teacher spread0.230 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it